Brian Gleeson

Effects of Platinum on the Interdiffusion and Oxidation Behavior of Ni-Al-Based Alloys

Thermal barrier coating (TBC) systems, needed for higher thrust with increased efficiency in gas turbines, typically consist of an alumina-scale forming metallic bond coat and a ceramic topcoat. The durability and reliability of TBC systems are critically linked to the oxidation behavior of the bond coat. Ideally, the bond coat should oxidize to form a slow-growing, non-porous and adherent thermally grown oxide (TGO) scale layer of α-Al2O3. The ability to promote such ideal TGO formation depends critically on the composition and microstructure of the bond coat, together with the presence of minor elements (metal and non-metal) that with time diffuse into the coating from the substrate during service. An experimental program was undertaken to attain a more detailed fundamental understanding of the phase equilibria in the Ni-Al-Pt system and the influences of alloy composition on the formation, growth and spallation behavior of the resulting TGO scales formed during isothermal and thermal cycling tests at 1150°C. Additional studies were conducted to determine the influence of platinum on interdiffusion behavior in the Ni-Al system, and how this influence would impact coating/substrate interdiffusion. It will be shown that platinum has a profound effect on the oxidation and interdiffusion behaviors, to the extent that novel advanced coating systems can be developed. Introduction The demand for improved performance in high-temperature mechanical systems has led to increasingly severe operating environments, particularly for the components in advanced gas-turbine engines. Future improvements in gas-turbine performance will require even higher operating efficiencies, longer operating lifetimes, reduced emissions and, therefore, higher turbine operating temperatures. Advanced cooling schemes coupled with thermal barrier coatings (TBCs) can enable the current families of nickel-base superalloys to meet the materials needs for the engines of tomorrow. Thermal barrier coating systems currently provide average metal temperature reductions of about 80°C, while potential benefits are estimated to be greater than 170°C. However, lack of reliability, more than any other design factor, limits the general use of TBC systems for gas turbines. Commercial advanced TBC systems are typically two-layered, consisting of a ceramic topcoat and an underlying metallic bond coat. The properties of the ceramic topcoat are such that it has a low thermal conductivity, high oxygen permeability, and a relatively high coefficient of thermal expansion. The topcoat is also made “strain tolerant” by depositing a structure that contains numerous pores and/or pathways. The consequently high oxygen permeability of the topcoat imposes the constraint that the metallic bond coat must be resistant to oxidation attack. The bond coat should therefore be sufficiently rich in aluminum to form a protective, thermally grown oxide (TGO) scale of α-Al2O3. In addition to imparting oxidation resistance, the TGO serves to bond the ceramic topcoat to the substrate/bond coat system. Notwithstanding, it is generally found that spallation and/or cracking of the growing TGO scale is the ultimate failure mechanism of Materials Science Forum Online: 2004-08-15 ISSN: 1662-9752, Vols. 461-464, pp 213-222 doi:10.4028/www.scientific.net/MSF.461-464.213

Factors Affecting Chromium Carbide Precipitate Dissolution During Alloy Oxidation

Ferrous alloys containing significant volumefractions of chromium carbides were formulated so as tocontain an overall chromium level of 15% (by weight) buta nominal metal matrix chromium concentration of only 11%. Their oxidation at 850°C inpure oxygen led to either protectiveCr2O3 scale formation accompaniedby subsurface carbide dissolution or rapid growth ofiron-rich oxide scales associated with rapid alloy surface recession, which engulfedthe carbides before they could dissolve. Carbide sizewas important in austenitic alloys: an as-castFe-15Cr-0.5C alloy contained relatively coarse carbides and failed to form aCr2O3 scale, whereas the samealloy when hot-forged to produce very fine carbidesoxidized protectively. In ferritic alloys, however, evencoarse carbides dissolved sufficiently rapidly to provide the chromium flux necessary to formand maintain the growth of a Cr2O3scale, a result attributed to the high diffusivity ofthe ferrite phase. Small additions of silicon to theas-cast Fe-15Cr-0.5C alloy rendered it ferritic and led toprotective Cr2O3 growth. However,when the silicon-containing alloy was made austenitic(by the addition of nickel), it still formed aprotective Cr2O3 scale, showing that the principal function of silicon was inmodifying the scale-alloy interface.

Oxidation Behavior of Pt+Hf-Modified γ-Ni +γ'-Ni3Al Alloys

The oxidation behavior of Pt+Hf-modified γ-Ni+γ′-Ni3Al alloys containing up to 20 at.% Pt and either 15 or 20 at.% Al was studied by oxidizing the alloys in air at 1150°C under both isothermal and thermal cycling conditions. It was found that the co-addition of Pt and Hf was extremely beneficial to oxidation resistance, to the extent that Ni-20Al-20Pt-Hf and Ni-20Al-10Pt-Hf alloys (all compositions are in at.%) oxidized at significantly slower rates than that of a Ni-50Al-15Pt β-NiAl alloy. A Ni-20Al-5Pt-Hf alloy also showed good oxidation resistance, with the steady-state oxidation rate being almost the same as that obtained for the β alloy. Over a period of up to 500 one-hour oxidation cycles, no oxide spallation from the modified γ+γ′ alloys was observed. From cross-sectional SEM examination coupled with X-ray diffraction analyses, it was found that a compact and planar exclusive scale layer of α-Al2O3 formed on the Ni-20Al-20Pt-Hf alloy. By contrast, the Ni-20Al-10Pt-Hf and Ni-20Al-5Pt-Hf alloys formed a very thin outer layer of NiAl2O4 and a planar inner layer of α-Al2O3. The thickness of the inner Al2O3 layer increased with increasing oxidation time relative to that of the NiAl2O4 layer, meaning that the latter primarily formed during the initial stages of scale formation. Both NiO and NiAl2O4 were found in the scales formed on the Ni-20Al-Hf and Ni-15Al-0~10Pt-Hf alloys, with the thickness of these oxide layers decreasing with increasing Pt content in the alloys. Further, it was found that the extent of internal HfO2 formation decreased significantly with increasing Pt content, to the extent that no HfO2 was found in the oxidized Ni-20Al-20Pt-Hf alloy. Inferences for the observed beneficial effects of Pt promoting protective Al2O3 formation and decreasing the tendency for Hf to oxidize in γ+γ′ alloys are discussed.

Pt and Hf Additions to NiAl Bond Coats and their Effect on the Lifetime of Thermal Barrier Coatings

The lifetimes of thermal barrier coatings (TBCs) with various NiAlPt(HfZr) bond coats were determined by cyclic oxidation testing at 1163 C (2125 F). The bond coats were sprayed from powders by low pressure plasma spraying onto Rene N5 superalloy substrates. Yttria stabilized zirconia (8YSZ) top coats were applied by air plasma spraying. Surprisingly, there was not a strong correlation between TBC lifetime and Pt or Hf content although Zr additions decreased lifetimes. TBC failure morphologies and bond coat microstructures were examined and are discussed with respect to the bond coat compositions.

Compositional Factors Affecting the Oxidation Behavior of Pt-Modified γ-Ni+γ’-Ni3Al-Based Alloys and Coatings

Many high-temperature coatings rely on the formation of a continuous and adherent thermally grown oxide (TGO) scale of α-Al2O3 for extended resistance to degradation. For instance, the durability and reliability of thermal barrier coating (TBC) systems in gas turbines are critically linked to the oxidation behavior and stability of an alumina-forming β-NiAl-based bond coat. This study focuses primarily on the development of unique Pt+Hf-modified γ′-Ni3Al+γ-Ni coating compositions that form highly adherent, slow-growing TGO scales during both isothermal and cyclic oxidation at high temperature. Recent findings on the isothermal and cyclic oxidation behavior of γ′+γ alloys and coatings will be discussed, with particular emphasis on the effects of Pt, Al and Hf contents and distributions. Inferred reasons for the observed “Pt effect” will also be presented.

Cyclic Oxidation of Chromia-Scale Forming Alloys: Lifetime Prediction and Accounting for the Effects of Major and Minor Alloying Additions

This paper briefly reviews methods to predict the useful service life of high temperature alloys exposed to thermal cycling conditions. Particular attention is given to chromia-scale forming alloys and the shortcomings are addressed of applying existing (and successful) models developed for alumina-scale forming alloys to chromia formers. The chromia-forming 800HT alloy is used to provide an example of the tractability of cyclic oxidation lifetime prediction. The oxidative effects of elements that are common minor and major additions to commercial, chromia-forming alloys are also discussed. The principal minor elements of concern are Si, Ti, Al, Mn, and reactive elements such as Ce, La, and Zr. It will be shown that variation of minor-element contents within the specified range of a given alloy can result in markedly different cyclic-oxidation behaviors. In most cases the oxidative effects of minor elements must be analyzed collectively rather than independently. An important consequence of this is that accurate modeling of oxidation performance must ultimately require an understanding of this apparent interdependence between the alloying elements. Introduction High temperature alloys derive their resistance to excessive oxidation attack by forming and maintaining a protective solid oxide scale layer. In order to exhibit good protective properties, the scale should be slow-growing, very stable, continuous, and adherent [1]. Most commercial alloys designed for high-temperature corrosion resistance rely upon the formation of either a chromia (Cr2O3) or alumina (Al2O3) scale. The growth of a protective scale is of finite duration, as the scale will eventually break down and the formation of a less protective scale will ensue. The time for scale breakdown is typically accelerated under thermal cycling conditions. Cyclic oxidation behavior is dictated mainly by scale adherence, which is affected by both scale morphology and alloy and scale compositions [2]. Moreover, because an oxide scale typically has a lower coefficient of thermal expansion (CTE) than the alloy substrate on which it forms, thermal stresses are induced during temperature variation. It is the combination of thermal stresses and poor scale adherence that causes the scale to crack and eventually break down under thermal cycling conditions. Breakdown marks the end of the useful service life of an alloy and, for a chromia-scale former, is a consequence of chromium depletion at the scale/alloy interface going below a critical concentration, NCr * , necessary for chromia-scale healing or reformation [3]. Fig. 1 shows the long-term oxidation behavior of various commercial alloys exposed to 1-day cyclic oxidation at 1000°C. There is a significant variation in oxidation behavior amongst the different Materials Science Forum Online: 2004-08-15 ISSN: 1662-9752, Vols. 461-464, pp 427-438 doi:10.4028/www.scientific.net/MSF.461-464.427

Mechanistic aspects of Pt-modified β-NiAl alloy oxidation

Abstract The effects of Pt addition (5, 10 and 15 at.%) on the high temperature oxidation behaviour of the intermetallic compound β-NiAl were studied at 1150°C under both isothermal and thermal cycling conditions. The scale growth mechanism was assessed using two-stage oxidation exposures with 18O2 as a tracer in conjunction with high-resolution secondary ion mass spectrometer analysis of isotopic distributions. The scale morphologies were further characterized using secondary electron microscopy, Pt was found to reduce slightly the scale growth rate and improve considerably its resistance to spallation but it did not affect the sequence of scale development. Instead, it slowed the rate at which the scale developed. The α-Al2O3 scales that were eventually established were duplex in structure, consisting of a compact inner layer and a thinner outer layer. This outer layer consisted of ridges and grew by the coarsening of these and/or by a dislocation climb mechanism.

Effects of Pt on the short-term oxidation behavior of γ-Ni+γ′-Ni3Al alloys

Abstract The aim of this study was to elucidate the beneficial role played by platinum addition in promoting the formation of a protective Al2O3 scale on γ′-Ni3Al+γ-Ni alloys during oxidation at high temperatures. To do this, the early-stage oxidation behavior of γ′-Ni3Al-based alloys of composition (in at.%) Ni–22Al and Ni–22Al with 10, 20, and 30 Pt was investigated in terms of oxidation kinetics, scale evolution and resulting composition profiles during heating to 1150°C in air. Platinum addition did not appear to affect the nature of the native oxide layer present on the γ′-based alloys at room-temperature; however, it was found that the presence of increasing Pt content aided in promoting the establishment of a continuous Al2O3 scale during heating above about 600°C. This beneficial effect can be primarily ascribed to the fact that Pt is non-reactive and its addition decreases the chemical activity of aluminum in γ′. Related to the latter, Pt partitions almost solely to the Ni sites in the ordered L12 crystal structure of γ′, which has the effect of amplifying the increase in the Al:Ni atom fraction on a given crystallographic plane containing both Al and Ni. Such an effective Al enrichment at the γ′ surface kinetically favors the formation of Al2O3 relative to NiO. A further contributing factor is that the Pt-containing γ′-based alloys showed subsurface Pt enrichment during the very early stages of oxidation. This enrichment reduces Ni availability and can increase the Al supply to the evolving scale, thus kinetically favoring Al2O3 formation.